Unsaturated triazine compounds



3,165,514 Patented Jan. 12, 1965 United States Patent Ofifice 3,165,514UNSATURATED TRIAZINE COMPOUNDS Gaetano F. DAlelio, South Bend, Ind,assignor, by direct and mesne assignments, to Dal Mon Research Co., -ICleveland, Ohio, a corporation of Delaware No Drawing. Filed Aug. '7,1962, Ser. No. 215,230 20 Claims. (Cl. 260248) This invention relates to.new compounds of the formula where n is an integer having a value of atleast one and no more than three; Z is a divalent radical predominantlyhydrocarbon, preferably having no more than 20 carbon atoms, R is anunsaturated hydrocarbon radical as defined more fully hereinafter; and Yrepresents a monovalent radical, preferably one selected from the classconsisting of hydrogen, hydrocarbon, halogen, RO, R'S-, R 'N-, wherein Ris hydrogen or a hydrocarbon radical preferably of no more than 12carbon atoms.

Compounds of the above structure are referredto hereinafter as triazinylvinyl compounds, or as tn'azine monomers. For purposes of simplicity,the trivalent 1,3,5-triazine, or symmetrical triazine nucleaus ishereinafter represented as C N This application is acontinuation-in-part of applicants copending application Ser. No.764,249, filed September 30, 1958 issued as Patent No. 3,050,496, August21, 1962.

In the triazinyl vinyl monomers of this invention Z is a divalenthydrocarbon radical and includes, for example, divalent aliphaticradicals, aromatic radicals, cycloaliphatic radicals, etc., variouscombinations of such radicals, such as alkaryl, aralkyl, etc., diaryloxides, diaryl sulfides, diaryl amines, etc., all of which radicals canalso have substituents thereon such as chloro, floro, alkoxy, acyloxy,etc. groups. Illustrative examples of divalent radicals that Z canrepresent in the above formula are:

CH3 CH3 Q2115 It-n CaH4NHCa 4; Ct 4OCsH4; -CsH4 Ca i- --CsH3NHC5H3-;-CsH3O-CsH5 -CaH3-; "C 7 H3 CH3 3H5 C211: 0 0511415 N(CH3)2 -CsH -CaHs-;etc I I THCsHr, N(CH:C5H5)2 The substituent groups such as the alkoxy,aryloxy, acyloxy, alkylarnino, arylamino, etc., radicals .areadvantageously radicals of no more than than about ten carbon atoms,such as methoxy, ethoxy, butoxy, pentoxy, octoxy, phenylmethoxy,phenylethoxy, acetoxy, propionoxy, butyroxy, valeroxy, capryloxy,benzoxy, phenylacetoxy, toluoxy, etc. Other groups, such as nitroso,nitro, etc., can also be used as substitutentson the Z group providedthey are inert during the preparation and use of the triazinyl vinylmonomer. The aliphatic group, or that portion of the Z group which isaliphatic, can be saturated or unsaturated, e.g. CH --CH=CH etc. Also,without departing from the spirit of this invention, the carbon atoms inthe divalent radical, Z, can be interrupted by an atom other thancarbon, e. g.

While other hydrocarbon and substituted hydrocarbon groups are alsoeffective as Z groups, Z preferably has no more than 18 carbon atoms andis selectedfrom the class of alkylene, cycloalkylene,alkenylene,naphthylene, diphenylene, diphenyleneoxide, diphenylenesulfide,diphenyleneamine, and derivatives thereof in which the derivative groupsare selected from the class of chloro, iiuoro, alkoxy, cycloalkoxy,alkenyloxy and acyloxy groups.

The triazinyl vinyl compounds of this invention can be Written as (M) (CN (Y) in which M represents the radical containing the polymerizablegroup, and the other symbols are as defined above. Where the monomercontains. only one polymerizable group, soluble, fusible polymers can beobtained. When the monomer contains two polymerizable groups, that is(M) is (M) 2 and the remaining or third group is the same or dilferentfrom the M group, insoluble,infusible polymers can be producedtherefrom. When (M), is (M) insoluble, infusible polymers and copolymerscan still be obtained where the Y group is any other polymerizable ornon-polymerizable monovalent radical. For example, Y can be hydrogen andalkyl, aryl, aralkyl, alkaryl, cycloaliphatic and heterocyclic groupsand their chloro, fluoro, alkoxy, aryloxy, acyloxy derivatives, such asmethyl, ethyl, propyl, isopropyl, butyl, octyl, decyl, chloroethyl,fluoropropyl, cyclohexyl, cyclopentyl, phenyl, chlorophenyl,fluorophenyl, xenyl, naphthyl, tolyl, isopropyl phenyl, benzyl,phenethyl, phenyl propyl, acetoxy benzyl, ethoxy propyl,. methylnaphthyl, vinyl, allyl, methallyl, allyl pheny, etc., radicals; Y canaso be hydroxyl and the alkoxy and aryloxy radicals derived fromaliphatic, cycloaliphatic, aromatic and heterocyclic hydroxy compoundssuch as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol,isobutyl alcohol, decyl' alcohol, phenol, the 0-, m-, and pcresols, thexylenols, naphthols, ethylene glycol, methyl glycol ether, butyl glycolether, glycerina, penta erythritol,

hydroxy napthalene, hydroxy pyridine, as well as the.

alkoxy and aryloxy radicals of hydroxy acids and esters such as lacticacids, ethyl lactate, salicylic acid, methyl NHC H SO NH NHC H SO NHCHetc. as shown in my US. Patent No. 2,212,697, issued March 2, 1943;radicals of acyl hydrazine and substituted hydrazines, such as CHCONHNH- C H CONHNC H C H SO NHNH etc. radicals of alkylene amines, suchas CHz-- CHz, H C-OHCH CGH5CH'OHH \NH \NH/ \NH/ Y can also be thepolymerizable radical of the acrylic,

methacrylic, chloracrylic ester or amide of amine alcohols or dialcoholsand diamines, e.g.

etc., the radicals of polymerizable aminated or hydroxylated alkenylenearyl compounds, for example etc., the radicals of malonic andsubstituted malonic esters, nitriles and amides, e.g.

HC(COOCH3), -HC(COOOH:CH==CH2)2, CH(ON)Z -OH[CON(CH3)2]2, HO

etc., the

o l (0R) radical such as etc., or the group can represent the remainderofthe molecule, for example,-(M) (C N )in compounds of the structure (M)(C N )(C 'N (M) as well as those 4 structures linked together throughcarbon atoms, sulfur atoms, oxygen atoms, etc., as for example )2( 3 a)2 2 a 3) 2 )2( a 3) 2 2 3 3) )2 )2( 3 3) 2 2 a s) b etc.

Thus, it may be seen that a wide variety of modified polymerizable vinylcompounds can be prepared in accordance with the practice of thisinvention and this modification is achieved by the nature of the Yradical, which can represent any monovalent radical.

When one of the groups attached to the triazinyl ring I contains apolymerizable ethylenic group which is not inhibited by the other atomsand groups in the monomer, then a soluble ,or fusible, orsoluble-fusible polymer is otbained on polymerizing the monomer. Suchmonomers can also be copolymerized with other monovinyl ormonovinylidene monomers, hereinafter generally referred to as vinylmonomers, such as acrylonitrile, methyl methacrylate, etc., to producemodified thermoplastic compositions. It has now been discovered thatwhen two or more polymerizable groups are attached to the triazine ring,insoluble,infusible, heat resistant, and in many casesself-extinguishing polymerization products are obtained. It has beenfurther discovered that the triazinyl-vinyl monomers of this inventioncan be copolymerized with other monoolefinic and polyolefinic monomersto, produce new materials having insolubility, infusibility, and heatresistanceand valuable and characteristic properties that make themespecially suitable for use in industry, for example, in molding,laminating, casting, coating, and

' adhesive applications, and for other purposes.

In accordance with this invention, homopolymers of the triazinyl vinylcompounds can be produced as well as compositions of matter comprisingan interpolymer (copolymer) or interpolymers of at least one triazinylvinyl compound of this invention and at least one other polymerizablecompound containing the structures or groupings More particularly, ithas been discovered that the triazinyl monomers of this invention areespecially useful for the preparation of copolymers with unsaturatedalkyd resins. As is well known, copolymers of the unsaturated alkydresins, for example, copolymers of styrene and glycol maleate have wideutility in industry for the preparation of reinforced laminates,radomes, etc. However, such products are limited in their applicationsby their poor resistance to heat, and are ineflective at relatively hightemperatures. Many attempts have been made to improve the heatresistance of such compositions, but with limited success.

It has now been discovered that these problems can be eliminated by theuse of certain triazinyl vinyl monomers of this invention which togetherwith the unsaturated alkyd give copolymerizable mixtures which haverapid rates of polymerization, together with high heat resistance,allowing such products to be used at relatively high temperatures. Suchproducts are disclosed in my copending application, Ser. No. 764,249,filed September 30, '1958.

Also, if solvent resistance is desired, this can be achieved byincreasing the nitrogen content or the hydroxyl content in the monomerin the groups attached to the triazine ring, or itself-extinguishingproperties are desired specifically, or in combination with heatresistance and solvent resistance, this can be accomplished byincreasing the nitrogen content, or the halogen content, or thephosphorus content in the groups attached to the triazine ring. Thus,with the new triazinyl vinyl monomers of this invention, a host of newuseful compositions can be prepared.

The monomers of this invention can also be added to preformed polymers,such as polacrylonitrile, polyethylene, polystyrene, cellulose acetate,polyvinyl acetate, and then polymerized while admixed with the polymerby added catalyst, or they'may be grafted to the polymer by irradiation,such as ionizing radiation from a cobalt or radioactive source, such asionizing radiation from a linear electron accelerator, etc. The symbol Rrepresents a terminally unsaturated hydrocarbon radical having a oHFC agrouping of the structure Chi C "-(CR" wherein m iszero or 1, and R" ishydrogen, halogen, or a hydrocarbon radical preferably of no more thancarbon atoms; Typical examples of R include wherein the symbols are asdefined above.

R represents hydrogen, or a saturatedor unsaturated monovalenthydrocarbon radical, such as the aliphatic, cycloaliphatic, aryl,aliphatic-substituted aryl, and arylsubstituted aliphatic, etc.radicals, for example, methyl, ethyl, vinyl, propyl, allyl, isopropyl,butyl, methallyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl,hexyl, octyl, crotyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, phenyl, diphenyl, xenyl, naphthyl, anthracyl,tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allyl phenyl,Z-butenyl, phenyl, propenylphenyl, tertiary-butylphenyl, methylnaphthyl,benzyl, cinnamyl, phenylethyl, phenylpropyl, etc., as well as aryl,aliphaticsubstituted aryl and aryl-substituted aliphatic radicals,wherein one or more of the hydrogen atoms of the hydrocarbon group hasbeen replaced by, for example, halogen, alkoxy, aryloxy, aralkoxy,alkaryloxy, acetoxy radicals, etc., such as chlorophenyl,dichlorophenyl, bromophenyl, dibromophenyl, methoxy phenyl, methoxy,naphthyl, acetoxy phenyl, benzoxy phenyl, methoxy ethyl, methoxy butyl,acryloxy ethyl, phenoxy phenyl, etc. Preferably, R is hydrogen, methyl,or phenyl.

Various methods can be employed to produce the triazinyl vinyl monomersof this invention. One method of preparing these new monomers compriseseffecting reaction between a halogenated triazine and MH, wherein M isthe radical containing the polymerizable group as indicated above, whichreaction is represented as follows, in each case using a hydrohalideacceptor such as sodium hydroxide: (C N )Cl +3MI-I (C N (M) +3HCl.

When it is desired to modify the monomer by the presence of a Y group,this can be accomplished by first introducing the M group andthen'introducing the Y groups, for example:

6 or if the Y groupis already attached to the triazine ring, then the Mgroup can be attached as for example: or the Y group can be introducedfirst, before introducing the M group,

as for example (C N )C1 +YH Y(C N )Cl +l-ICl The reaction can begeneralized further by the equation )3n( 3 3) )n+ )3-n( 3 3) M and inthe above equations halogen derivatives other than the chloride can alsobe used, and n, M and Yhave the same meaning given hereinabove. Thesereactions can be carried out in an anhydrous liquid medium such asether, benzene, dioxane, acetone, etc., or in water or in mixtures ofwater with water-soluble solvents such as acetonedioxane preferably inthe presence of anhydrohalide acceptor such as sodium hydroxide,potassium hydroxide, sodium bicarbonate, sodium carbonate, pyridine,tributyl amine, etc., and at temperatures from below or about roomtemperature to temperatures corresponding to the refluxing temperatureof the solvent or'mixture of reactants. v

Illustrative examples of halogenated triazine intermediates that can beused in the preparation of triazine monomers include the following: 7

(CaN3) C13; (CsNQBrz; (CaNsfia; HO(CaNs) C12; H0(CaNa)Br z H2N(C3Ns)C12; (CH3)2N(C3N3)C12; (C2H5)2N(C3Ns) C12 CH3O(C3N3)CI2; C2H5O(CaNs)Br2;CH2=CHCHzO(C3N3)C12 UHF? CHz-(C3Na) C12; H(C3Na) C12; C2H5(CaNa) C13071350 ONHCHzCHzN'BKCNa) C12; CsHzC O 0 CHzCHzO (CaNa) C12 (CHaO)zP O(CzNa) C12; (CHFGHCHQO) P O (CaNa) C12 ClCaH-iNH(CaNa) on; 01130CaH4NH(O3Ns) on 1 (H1300 ooimtogNi) on; me o o OCHzNH(C3Na)CliHzNOzSCaH4N'H(C3N3)C1z; onzo GHQO can) on These intermediates can beprepared by various methods reported in the literature for replacing thehalogen atoms in. halo triazines, such as cyanuric chloride, withvarious groups such as hydrocarbon groups, alkoxy, aryloxy,

substituted amino groups, mercapto, alkylthio, hydroxy, hydrogen, etc.'By using the appropriate reagents with 'such halo-triazines, thevarious intermediates desired for preparing the compounds of thisinvention can be pre pared following procedures taught in the following"references; a

For introducing NR' groups:

Thurston et al.: Iourn. of ;A-merican Chemical Soc., 73,

Thurston et' al.: Journ. of American 'ChemicalSoc, 73,

For introducing alkoxy groups:

-Dudley et al.: I.A.C.S., 73, 2986 (1951); ,Diels 61131.1]3611, 36, 3191(1903);

Hoiiman: Ber., 19, 2061' (1886); DAlelio: U.S. Patent 2,295,562;

For introducing aryloxy groups:

Schaefer ct all J.A.C.S., 73, 2990 (1951);

Klason: J. prakt. Chem., (2) 34, 152 (1886);

Hoffman: Ber., 18, 2196 (1885); Ciba British Patent 318,275 (1930);DAlelio et al.: U.S. Patents 2,295,561 and 2,295,562;

For introducing hydrocarbon groups:

For introducing hydrogen:

Ben: 32, 691 (1899); Hirt et al.: Helv. chim. Acta, 33, 1365 (1950);

' Illustrative examples of MH compounds that can be used asintermediates in the preparation of the triazine monomers include:

HO CHQG 0 CH=CH;- HO 011200 0 0:013?

HO 011200 0 CHzCH=CH2; HO 01120 0 o OHZCT-CHI I T/Ha HO (315120 0 OOH(L=OHz; HO (CHZ)4C O O CHzOH=CH2 The monomers of this invention canalso be prepared by reacting the free acid with an alcohol, ROI-I toproduce the esters; by reacting the free acid with acetylene orsubstituted acetylenes to produce vinyl and substituted vinyl compoundsaccording to well known procedures for making vinyl esters; or by esterexchange of a lower ester, such as a methyl or ethyl ester, with anunsaturated alcohol, as for example, allyl alcohol, methallyl alcohol,etc.

In these syntheses, the temperature is usually maintained at below 100C. and preferably in the presence of a polymerization inhibitor.

This invention will be more fully described by the following examples.The invention is not to be regarded, however, as restricted in any wayby theseexamples and they are to serve merely as illustrations. In theseexamples, as Well as throughout the specification, parts and percentagesshall mean parts by weight and percentages by weight unless specificallyprovided otherwise.

EXAMPLE Preparation of Triazine Monomers To 5 3.2 parts of allylpara-hydroxy-benzoate, in a flask equipped with means for refluxing, and12 parts of sodium hydroxide in 200 parts of Water is added slowly andwith stirring 18.4 parts of cyanuric chloride in 50 parts of acetone.Upon completion of the addition of the chloride, there is added 1 partof 2,4-diisobutyl paracresol, and the mixture, is refluxed for about 4hours and allowed to cool to room temperature. Thereafter, the mixtureis filtered to remove the solid monomer. The monomer is washed withwater and is crystallized from acetonewater mixtures. There is obtainedthe ester Ultimate analyses for carbon, hydrogen, nitrogen, andmolecular weight determination give values of 62.1%, 4.79%, 7.65%, and557.6 respectively, all of which are in close agreement with thetheoretical values. Substitution of an equivalent amount of for thecyanuric chloride in the above procedure yields the correspondingtriazine monomer of the formula 8 Ultimate, analyses and molecularweight determination give 66.1% carbon, l0.l% nitrogen, 6.35% hydrogen,and a molecular weight of 562, all of which check closely with thetheoretical values. Use of an equivalent amount of [(C H N] C N Cl inthe above procedure yields the corresponding triazine monomer of theformula In a similar manner, there are prepared the monomers listedhereinafter.

They are also prepared by an esterification reaction as in the followingprocedure. 7

A mixture of 200 parts of benzene, '31 parts of tri-(carboxymethoxy)triazine, C N (OCH COOH) 25 parts of allyl alcohol, and0.2 parts of toluene sulfonic acid, are reacted in a continuousesterification apparatus until no more water of esterification iseliminated. The mixture is then washed with 10% sodium carbonate-aqueoussolution until the aqueous layer is alkaline and then with water toneutrality and freedom from salts. The benzene is then removed underreduced pressure, leaving the triazine monomer of the formula (C N (GCHCOOCH CH=CH 3 which is recrystallized from acetone-water mixtures.Analyses for carbon, hydrogen, and nitrogen give values in closeagreement with the theoretical values. Substitution in the aboveprocedures by other triazinyl oxy acids, for example, by

CHCOOH CQHKOQMOOQQGOOHM 0 CH3 CeH5-(|1aNa-O (CH2)5C O OH etc., in theforegoing procedure produces the corresponding monomers, whereasreplacement of the allyl alcohol by other alcohols, such as (1H3 (3H3CHFC-CHZOH, CHFCH-CHOH etc., produces the corresponding triazinemonomer.

By these procedures, various monomers of this invention are preparedwhich have the following formulas:

C1 CeHCQN H-G3N3OC3H4QoQCH2CH=CHz The monomers of this invention arechemical compounds which can also be used as chemical intermediates forthe preparation of new compounds which can have utility other than inthe preparation of polymers. As an example, these monomeric compoundscan be halogenated to produce the chloro or bromo derivatives, etc., asillustrated by the reaction CHaO(l33N3-O 01120 O O OH2CH=CHz+BrH ClGH3O?;;N3-O CHzCOOCHzCHBICHzBI 01 When the monomer has 2 or 3unsaturated groups the halogenation can be limited so as to leave onesuch unsaturated group and give a product which can be polymerized, suchas C1-CaN3-O CH2CO0CH2CH=CH2 OCHrCOOCHzCHBrCHaBr 0 01320 O O CH2CH=CH2ClCaNs-O Ca 4C O O CHzOHClCHzCl O CaHrC O O OH2CH=CH2 CaN3(O 054C 0 OCHzCHClCHaCDa CaN3(O CsHiC O O CHzCHBtCHzBI):

These monomers can be epoxidized with H 0 and an acid according to wellknown procedures to give compounds such as 1Q These derivatives can beused as hydrohalide acceptors, intermediates in the preparation ofadhesives and for the preparation of varnishes, paints, etc.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above, except insofar as they are defined inthe following claims: I

The invention claimed is:

1. A triazine compound of the formula wherein:

n is an integer having a value of at least 1 and no more than 3;

Z has no more than 18 carbon atoms and is selected from the classconsisting of alkylene, cyclohexylene, alkylene, phenylene, naphthylene,.diphenylene, diphenyleneoxide, diphenylenesulfide, anddiphenyleneamineand derivatives'thereof in which there is only onederivative group therein and said derivative group is selected from theclass consisting of chloro, fluoro, alkoxy, pheny-lalkoxy, alkenoxy andhydrocarbon carboxylic acyloxy groups;

R" is selected from the class of hydrogen, halogen and hydrocarbon of nomore than 10 carbon atoms; a

m is an integer having a value of at least 0 and no more than 1;

Y has no more than 18 carbon atoms and is selected from the classconsisting of halogen, -OR', -NR' -SR', alkenyl, alkyl, aryl, havingonly benzene nuclei, cyclohexyl and cyclopentyl;

R is selected from the class consisting of hydrogen and hydrocarbon ofno more than 8 carbon atoms; and

C N represents cleus. 2. The triazine compound of the formula C N (OC HCOOCH CH=CH 3. The triazine compound of the formula (C 11 N-C N (OC HCOOCH CH=CH 2 The triazine compound of the formula (Cg-I N] C N -OC HCOOCH CH=CH 5. The triazine compound of the formula C N (OCH COOCHCH==CH 3 6. The triazine compound of the formula C N (OCH COOCH =CH Thetriazine compound of the formula CH OC N (OC H COOCH CH=CH 2 8. Thetriazine compound of the formula (C4H9);NC3N3[O (crime 0 0 CHz(|J=CH thetrivalent symmetrical triazine nu- 9. The triazine compound of theformula C H --C N (OC H COOCH CH=CH 2 10. The triazine compound of theformula 11. The triazine compound of the formula 12. The triazinecompound of the formula (CH;)gN-(|33Nr0 onto 0 o ornorr=om The 'triazinecompound of the formula The triazine compound of the formula 7 CH30 C3N30 CHzC O O CHaCHBrCHzBr The triazine compound of the formula Thetriazine compound of the formula C3Na(0 (11120 O 0 0112011 01011201): 0011200 0 angel-1:011;

19. The trlazine compound of the formula C3Na(0 cmoooomoumomnmOOHzCOOQHzCH=GH 20. The triazine compound of the formula (C H NC N (OCHC0OCH CH -CH References Cited by the Examiner UNITED STATES PATENTSDAlelio et al. 260-2495 DAlelio et a1. 260-2498 Bernstein et a1.260-249.6 Layman 260-249.8 Randall et a1 260-2495 Frazier et al.260-2493 DAlelio 260-2495 DAlelio 260-2496 DAlelio 260-248 DAlelio260-2496 IRVING MARCUS, Primary Examiner.

JOHN D. RANDOLPH, WALTER A. MODANCE,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF GOR'RECTION Patent Nos3,165,514 January 12, 1965 Gaetano F, D'Alelio tified that error appearsin the above numbered pat- It is hereby oer t the said Letters Patentshould read as ent requiring correction and tha correotedbelow.

Column 10, lines 13 and 14, the formula should appear as shown belowinstead of as in the patent:-

Y {c N H0-z-c0o(cR cR=cH 1 S-n 3 3 2 m 2 n Signed and sealed this 14thday of September 1965.,

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents ERNEST W. SWIDER AIM-stingOfficer

1. A TRIAZINE COMPOUND OF THE FORMULA